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At \(35^{\circ} \mathrm{C}\) the vapor pressure of acetone, \(\left(\mathrm{CH}_{3}\right)_{2} \mathrm{CO},\) is 47.9 \(\mathrm{kPa}\), and that of carbon disulfide, \(\mathrm{CS}_{2}\), is \(66.7 \mathrm{kPa}\). A solution composed of an equal number of moles of acetone and carbon disulfide has a vapor pressure of \(86.7 \mathrm{kPa}\) at \(35^{\circ} \mathrm{C} .(\mathbf{a})\) What would be the vapor pressure of the solution if it exhibited ideal behavior? (b) Based on the behavior of the solution, predict whether the mixing of acetone and carbon disulfide is an exothermic \(\left(\Delta H_{\text {soln }}<0\right)\) or endothermic \(\left(\Delta H_{\text {soln }}>0\right)\) process.

Short Answer

Expert verified
(a) 57.3 kPa is the ideal vapor pressure. (b) The mixing is endothermic, \( \Delta H_{\text{soln}} > 0 \).

Step by step solution

01

Define Ideal Behavior

For a solution exhibiting ideal behavior, the vapor pressure can be found using Raoult's Law: \[ P_{ ext{solution}} = X_{ ext{acetone}} \cdot P_{ ext{acetone}}^0 + X_{ ext{CS}_2} \cdot P_{ ext{CS}_2}^0 \]where \( X \) is the mole fraction and \( P^0 \) is the pure component's vapor pressure.
02

Calculate Mole Fractions

Since we have an equal number of moles of acetone and carbon disulfide, the mole fractions for each component are both \( X_{ ext{acetone}} = X_{ ext{CS}_2} = 0.5 \).
03

Calculate Ideal Vapor Pressure

Substituting the mole fractions and vapor pressures into Raoult's Law gives:\[P_{ ext{solution}} = 0.5 \cdot 47.9 \, \text{kPa} + 0.5 \cdot 66.7 \, \text{kPa} \]\[P_{ ext{solution}} = 23.95 \, \text{kPa} + 33.35 \, \text{kPa} = 57.3 \, \text{kPa}\]Thus, the ideal vapor pressure is 57.3 kPa.
04

Compare with Actual Vapor Pressure

The actual vapor pressure of the solution is 86.7 kPa, which is higher than the ideal vapor pressure of 57.3 kPa. This indicates a deviation from ideal behavior.
05

Determine Enthalpy Change

Since the actual vapor pressure is greater than the ideal, this suggests the solution exhibits positive deviation from ideality. Positive deviation is typically associated with an endothermic mixing process, where \( \Delta H_{\text{soln}} > 0 \).

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Key Concepts

These are the key concepts you need to understand to accurately answer the question.

Vapor Pressure
Vapor pressure is a measure of how much a liquid's particles tend to escape into the gas phase. It's the pressure exerted by a vapor in equilibrium with its liquid at a given temperature. For instance, in your exercise, acetone and carbon disulfide have their own vapor pressures defined at 35°C: 47.9 kPa and 66.7 kPa, respectively.
Understanding vapor pressure is crucial because it helps predict how a liquid will behave when mixed with another. A high vapor pressure indicates that the substance evaporates easily, while a low vapor pressure suggests it's less volatile. When you combine two liquids, their individual vapor pressures contribute to the overall vapor pressure of the mixture. This forms the basis of Raoult's Law, blending in their mole fractions as next steps show, to determine the behavior of solutions under ideal conditions.
Ideal Behavior
When we talk about ideal behavior in solutions, we're discussing how substances act when they completely follow theoretical predictions, specifically Raoult's Law.
According to Raoult’s Law, the vapor pressure of an ideal solution equals the sum of the individual vapor pressures of the components, each weighted by its mole fraction. Mathematically, it's expressed as:
  • \( P_{\text{solution}} = X_{\text{acetone}} \cdot P_{\text{acetone}}^0 + X_{\text{CS}_2} \cdot P_{\text{CS}_2}^0 \)
The exercise asks us to calculate the vapor pressure assuming ideal behavior. By computing the weighted contributions of each component's vapor pressure, we determine the theoretical vapor pressure of a perfect mixture.
Ideal behavior assumes no interaction beyond individual contributions, meaning the molecules don't attract or repel each other. This setting is extremely instrumental in understanding deviations as well, where real solutions show differences because of molecular interactions not accounted for in the ideal scenario.
Mole Fraction
Mole fraction is a way to express the concentration of a component in a mixture. It conveys the number of moles of a component relative to the total moles in the mixture. It's a dimensionless quantity, calculated by dividing the moles of one component by the total number of moles in the solution.
In the exercise, the solution comprises equal moles of acetone and carbon disulfide, which leads us to straightforwardly define their mole fractions as both 0.5. This simplicity eases the calculations when applying Raoult's Law. The mole fraction essentially relays the proportionate presence and contribution of each substance to overall properties, such as vapor pressure.
Understanding mole fractions is key because it directly relates the pure component properties to the mixed behavior of solutions. The deviation in expected outcomes often hints at complex interactions and paves the way to explore further thermal effects, like exothermic or endothermic processes, as seen in your original problem set.

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Most popular questions from this chapter

Indicate whether each statement is true or false: (a) If you compare the solubility of a gas in water at two different temperatures, you find the gas is more soluble at the lower temperature. (b) The solubility of most ionic solids in water decreases as the temperature of the solution increases. (c) The solubility of most gases in water decreases as the temperature increases because water is breaking its hydrogen bonding to the gas molecules as the temperature is raised. (d) Some ionic solids become less soluble in water as the temperature is raised.

The maximum allowable concentration of lead in drinking water is 9.0 ppb. (a) Calculate the molarity of lead in a 9.0 ppb solution. (b) How many grams of lead are in a swimming pool containing 9.0 ppb lead in \(60 \mathrm{~m}^{3}\) of water?

The vapor pressure of pure water at \(70^{\circ} \mathrm{C}\) is \(31.2 \mathrm{kPa}\). The vapor pressure of water over a solution at \(70^{\circ} \mathrm{C}\) containing equal numbers of moles of water and glycerol \(\left(\mathrm{C}_{3} \mathrm{H}_{5}(\mathrm{OH})_{3}\right.\), a nonvolatile solute) is \(13.3 \mathrm{kPa}\). Is the solution ideal according to Raoult's law?

Soaps consist of compounds such as sodium stearate, \(\mathrm{CH}_{3}\left(\mathrm{CH}_{2}\right)_{16} \mathrm{COO}^{-} \mathrm{Na}^{+},\) that have both hydrophobic and hydrophilic parts. Consider the hydrocarbon part of sodium stearate to be the "tail" and the charged part to be the "head." (a) Which part of sodium stearate, head or tail, is more likely to be solvated by water? (b) Grease is a complex mixture of (mostly) hydrophobic compounds. Which part of sodium stearate, head or tail, is most likely to bind to grease? (c) If you have large deposits of grease that you want to wash away with water, you can see that adding sodium stearate will help you produce an emulsion. What intermolecular interactions are responsible for this?

Two nonpolar organic liquids, benzene \(\left(\mathrm{C}_{6} \mathrm{H}_{6}\right)\) and toluene \(\left(\mathrm{C}_{7} \mathrm{H}_{8}\right),\) are mixed. (a) Do you expect \(\Delta H_{\text {soln }}\) to be a large positive number, a large negative number, or close to zero? Explain. (b) Benzene and toluene are miscible with each other in all proportions. In making a solution of them, is the entropy of the system increased, decreased, or close to zero, compared to the separate pure liquids?

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